JP2004359930A - Liquid resin composition, cured film and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid resin composition for efficiently producing a lower refractive index layer and a higher refractive index layer and provide a cured film and a laminated product. <P>SOLUTION: The liquid resin composition comprises (A) a fluorine-containing polymer, (B) a curing compound, (C) metal oxide particles having ≤100 nm number average particle size and (D) a solvent. When the composition is cured, the metal oxide particles (C) deviate to change the refractive index in the depth direction in 0.05-0.8. Therefore, the cured film substantially having a double layer structure with the lower refractive index layer and the higher refractive index layer is produced. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a liquid resin composition, a cured film, and a laminate, and particularly, a liquid resin composition, a cured film, and a cured film having a low refractive index layer and a high refractive index layer, which can be formed by a single coating step. It relates to a laminate.

  At present, with the development of multimedia, various developments are being made in various display devices (display devices). Among various types of display devices, in particular, those that are used outdoors, mainly for portable use, are becoming more and more important to improve the visibility of the display devices. It is required by the consumer, and this matter is a technical issue as it is.

  Conventionally, as one means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device, and a method of forming the antireflection film is used. For example, a method of forming a thin film of a fluorine compound by a vapor deposition method is known. However, in recent years, there has been a demand for a technique capable of forming an anti-reflection film on a large-sized display device at low cost, mainly for a liquid crystal display device. However, in the case of using the vapor deposition method, it is difficult to form a uniform antireflection film with high efficiency on a large-area substrate, and the cost is reduced because a vacuum device is required. Have difficulty.

  Under such circumstances, a method of forming a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent, and applying this to the surface of a substrate to form an antireflection film has been studied. I have. For example, it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate (for example, see Patent Documents 1 and 2). Also, a method of applying a fluoropolymer having a specific structure has been proposed (for example, see Patent Document 3).

JP-A-61-40845 Japanese Patent Publication No. Hei 6-98703 JP-A-6-15023

These conventional antireflection films made of a fluorine-based material require that a low-refractive-index layer made of a fluorine-based material be formed on a high-refractive-index layer provided on a base material, and a coating for forming these layers is performed. The steps had to be provided separately.
Further, the scratch resistance of the low refractive index layer as the surface layer was not sufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid resin composition capable of efficiently producing a low refractive index layer and a high refractive index layer. It is another object of the present invention to provide a cured film having high transparency, high adhesion to a substrate, and excellent scratch resistance and dust wiping properties.

The liquid resin composition of the present invention is characterized by containing the following components (A), (B), (C) and (D).
(A) Fluoropolymer (B) Curable compound (C) Metal oxide particles having a number average particle diameter of 100 nm or less (D) Solvent

  The cured film of the present invention is obtained by curing the above liquid resin composition.

  The method for producing a cured film according to the present invention includes a step of curing the liquid resin composition by heating or irradiating the liquid resin composition with radiation.

  The laminate of the present invention is characterized by having a layer composed of the above cured film and a substrate.

  The cured film obtained by curing the liquid resin composition of the present invention can form a low-refractive-index layer and a high-refractive-index layer in a single application step, so that a cured film having a two-layer structure is produced. The process can be simplified. Therefore, the liquid resin composition of the present invention can be advantageously used particularly for forming an optical material such as an antireflection film and an optical fiber sheath material, and is required to have weather resistance by utilizing its high fluorine content. It can be suitably used as a material for a paint, a material for a weather-resistant film, a material for a coating, etc. for a substrate to be formed. Moreover, the cured film has excellent adhesion to the substrate, has high scratch resistance, and imparts a good antireflection effect, and thus is extremely useful as an antireflection film. And its visibility can be improved.

1. Liquid resin composition The liquid resin composition of the present invention contains the following components (A), (B), (C) and (D).
(A) Fluoropolymer (B) Curable compound (C) Metal oxide particles having a number average particle diameter of 100 nm or less (D) Solvent These components will be described below.

(A) Fluorine-containing polymer The fluorine-containing polymer is a polymer having a carbon-fluorine bond in a molecule, and has a fluorine content of 30% by weight or more. As preferred examples of the fluoropolymer, any fluoropolymer having a hydroxyl group in the molecule can be suitably used. Preferred examples of the fluorinated polymer include those having a polysiloxane segment in the main chain containing 10 to 50 mol% of a structural unit derived from a monomer having a hydroxyl group. The fluorine-containing polymer preferably has a fluorine content of 30% by weight or more and a number average molecular weight in terms of polystyrene of 5000 or more. This fluorinated polymer is an olefin polymer having a polysiloxane segment represented by the following general formula (1) in the main chain, and the proportion of the polysiloxane segment in the fluorinated polymer is usually 0.1 to 20 mol%.

式中、Ｒ^１及びＲ^２は、同一でも異なってもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す。

In the formula, R ¹ and R ² may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.

  The fluorine-containing polymer preferably has a fluorine content of 30% by weight or more, more preferably 40 to 60% by weight, and further has a number average molecular weight in terms of polystyrene obtained by gel permeation chromatography, preferably It is 5,000 or more, more preferably 10,000 to 500,000. Here, the fluorine content is a value measured by the alizarin complexon method, and the number average molecular weight is a value when tetrahydrofuran is used as a developing solvent.

  The fluoropolymer includes (a) a fluorine-containing olefin compound (hereinafter, referred to as “component (a)”), and (b) a monomer compound having a hydroxyl group copolymerizable with the component (a) (hereinafter, referred to as “component (a)”). "(B) component") and (c) an azo group-containing polysiloxane compound (hereinafter referred to as "(c) component") and, if necessary, (d) a reactive emulsifier (hereinafter "(d) And / or (e) a monomer compound other than the component (b) copolymerizable with the component (a).

  Examples of the fluorine-containing olefin compound as the component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Specific examples thereof include, for example, (1) fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene; (2) perfluoro (alkyl vinyl ether) s or perfluoro (alkoxyalkyl vinyl ether) s; (3) perfluoro (methyl) Perfluoro (alkyl vinyl ether) s such as vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), and perfluoro (isobutyl vinyl ether); (4) perfluoro (propoxypropyl vinyl) Ether) such as perfluoro (alkoxyalkyl vinyl ethers); other can be exemplified. These compounds can be used alone or in combination of two or more. Among them, hexafluoropropylene, perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is particularly preferable, and it is more preferable to use them in combination.

  Examples of the monomer compound having a hydroxyl group as the component (b) include (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 3-hydroxybutyl. Hydroxyl-containing vinyl ethers such as vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; (2) hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; 3) Allyl alcohol; (4) hydroxyethyl (meth) acrylate; and others. These compounds can be used alone or in combination of two or more. Preferred are hydroxyl group-containing alkyl vinyl ethers.

  As the azo group-containing polysiloxane compound of the component (c), a compound containing an easily thermally decomposable azo group represented by -N = N- and having a polysiloxane segment represented by the general formula (1) For example, it can be manufactured by the method described in JP-A-6-93100. Specific examples of the component (c) include a compound represented by the following general formula (2).

式中、ｙ＝１０〜５００、ｚ＝１〜５０である。

In the formula, y = 10 to 500 and z = 1 to 50.

  Preferred combinations of the above components (a), (b) and (c) are, for example, (1) a fluoroolefin / hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane unit, (2) a fluoroolefin / perfluoro (alkyl vinyl ether) / Hydroxyl-containing alkylvinyl ether / polydimethylsiloxane unit, (3) fluoroolefin / perfluoro (alkoxyalkylvinylether) / hydroxyl-containing alkylvinylether / polydimethylsiloxane unit, (4) fluoroolefin / perfluoro (alkylvinylether) / hydroxyl-containing alkylvinylether / Polydimethylsiloxane unit, (5) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane It is a down unit.

  In this fluoropolymer, the structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, and particularly preferably 30 to 60 mol%. When the proportion of the structural unit derived from the component (a) is less than 20 mol%, the fluorine content in the obtained fluoropolymer tends to be too low, and the cured product of the obtained liquid resin composition has a sufficiently low refractive index. It is difficult to become things. On the other hand, when the proportion of the structural unit derived from the component (a) exceeds 70 mol%, the solubility of the obtained fluoropolymer in an organic solvent is significantly reduced, and the obtained liquid resin composition has transparency. And the adhesiveness to a base material becomes small.

  In the fluorinated polymer, the structural unit derived from the component (b) is preferably from 10 to 50 mol%. More preferably, the lower limit is 13 mol% or more, further preferably more than 20 mol%, and 21 mol% or more, and preferably the upper limit is 45 mol% or less, and further preferably 35 mol% or less. It is. By composing the liquid resin composition using the fluoropolymer containing the component (b) in a predetermined amount, the cured product can achieve good scratch resistance and dust wiping properties. On the other hand, when the proportion of the structural unit derived from the component (b) is less than 10 mol%, the solubility of the fluorine-containing polymer in an organic solvent becomes poor, and when it exceeds 50 mol%, the fluorinated polymer becomes a liquid resin composition The cured product has poor transparency and low reflectance optical characteristics.

  The azo group-containing polysiloxane compound as the component (c) is a thermal radical generator itself, and has an action as a polymerization initiator in a polymerization reaction for obtaining a fluoropolymer. They can be used together. The proportion of the structural unit derived from the component (c) in the fluoropolymer is preferably such that the polysiloxane segment represented by the general formula (1) is 0.1 to 20 mol%, and more preferably 0.1 to 15 mol%. Mol%, particularly preferably 0.1 to 10 mol%, particularly preferably 0.1 to 5 mol%. When the proportion of the polysiloxane segment represented by the general formula (1) is more than 20 mol%, the obtained fluoropolymer has poor transparency. Occasionally, cissing and the like easily occur.

  In addition to the components (a) to (c), it is preferable to use a reactive emulsifier as a monomer component as the component (d). By using the component (d), when the fluoropolymer is used as a coating agent, good coating properties and leveling properties can be obtained. As this reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier. Specific examples of the nonionic reactive emulsifier include, for example, a compound represented by the following general formula (3) or (4).

式中、ｎ、ｍ及びｓは、繰り返し単位を示し、ｎ＝１〜２０、ｍ＝０〜４、ｓ＝３〜５０である。

In the formula, n, m and s represent a repeating unit, where n = 1 to 20, m = 0 to 4, and s = 3 to 50.

式中、ｍ及びｓは、一般式（３）と同様である。Ｒ^３は、直鎖状でも分岐状でもよいアルキル基であり、好ましくは炭素数１〜４０のアルキル基である。

In the formula, m and s are the same as in the general formula (3). R ³ is an alkyl group which may be linear or branched, and is preferably an alkyl group having 1 to 40 carbon atoms.

  In the fluorinated polymer, the proportion of the constituent unit derived from the component (d) is preferably 0 to 10 mol%, more preferably 0.1 to 5 mol%, and particularly preferably 0.1 to 1 mol%. is there. If this proportion exceeds 10 mol%, the resulting liquid resin composition becomes tacky, which makes it difficult to handle and reduces the moisture resistance when used as a coating agent.

  Examples of the monomer compound (e) other than the component (b) copolymerizable with the component (a) include (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Alkyl vinyl ethers or cycloalkyl vinyl ethers such as isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; (2) vinyl acetate Vinyl carboxylate esters such as, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate; ) Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n- (Meth) acrylic esters such as (propoxy) ethyl (meth) acrylate; (4) carboxyl group-containing monomer compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; And those containing no hydroxyl group. Preferably, it is an alkyl vinyl ether.

  In the fluorinated polymer, the proportion of the constituent unit derived from the component (e) is preferably 0 to 70 mol%, more preferably 5 to 35 mol%. If this proportion exceeds 70 mol%, the resulting liquid resin composition becomes tacky, and thus it becomes difficult to handle, and when used as a coating agent, the moisture resistance decreases.

When component (d) is contained, preferred combinations of component (a), component (b), component (c), component (d) and component (e) are as follows.
(1) fluoroolefin / hydroxyl-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (2) fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / Alkyl vinyl ether, (3) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (4) fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group-containing vinyl ether / Polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (5) fluoroolefin / perfluoro (A Job Shi alkyl vinyl ether) / hydroxyl group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether.

  Examples of the radical polymerization initiator that can be used in combination with the component (c) include (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; and (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide. Oxides; (3) Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide; (4) Hydroperoxides such as di-tert-butyl peroxide, dicumyl peroxide and dilauroyl peroxide Dialkyl peroxides; (5) peroxyesters such as tert-butylperoxyacetate and tert-butylperoxypivalate; and (6) azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Compounds like; (7) ammonium persulfate, sodium persulfate, persulfates such as potassium persulfate; Other can be exemplified.

  Specific examples other than the above radical polymerization initiator include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, (Perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro -2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane And the like. The iodine-containing fluorine compound can be used alone or in combination with the above organic peroxides, azo compounds or persulfates.

  As a polymerization mode for producing a fluorine-containing polymer, using a radical polymerization initiator, any of emulsion polymerization, suspension polymerization, bulk polymerization or solution polymerization can be used. , Batch, semi-continuous or continuous operation, and the like.

  The polymerization reaction for obtaining the fluoropolymer is preferably performed in a solvent system using a solvent. Here, preferred organic solvents include, for example, (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve acetate; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) cyclic ethers such as tetrahydrofuran and dioxane; (4) amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) aromatic hydrocarbons such as toluene and xylene; and others. be able to. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.

  The fluoropolymer obtained as described above may be able to use the reaction solution obtained by the polymerization reaction as it is as a liquid resin composition as it is. You are also free to do. As this post-treatment, for example, a general reprecipitation treatment typified by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the fluoropolymer, such as alcohol, to solidify the fluoropolymer. And then dissolving the resulting solid copolymer in a solvent to prepare a solution of the fluoropolymer. Further, a solution obtained by removing the residual monomer from the polymerization reaction solution can be used as it is as a solution of the fluoropolymer.

(B) Curable Compound In the liquid resin composition, the curable compound may be simply included as a mixture with the fluoropolymer, or may be a reaction product obtained by reacting all of the fluoropolymer and the curable compound. A state in which only a part thereof is reacted may be included.

  Examples of the curable compound include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and the like.

  The amino compound used as the curable compound contains an amino group capable of reacting with a hydroxyl group present in the fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total of two or more. Specific examples thereof include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specifically include melamine, alkylated melamine, methylolmelamine, alkoxylated methylmelamine, and the like. Although it is possible, one having one or both of a methylol group and an alkoxylated methyl group in one molecule in total is preferable. Specifically, a methylolated melamine, an alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and a good storage stability is particularly obtained in a liquid resin composition. In view of this point and good reactivity, alkoxylated methylmelamine is preferred. There are no particular restrictions on the methylolated melamine and the alkosylated methylmelamine used as the curable compound, and for example, they can be obtained by the method described in the literature “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). It is also possible to use various kinds of resinous materials.

  Examples of the urea-based compound include, in addition to urea, polymethylolated urea and its derivatives, alkoxylated methylurea, methylolated uron having a urone ring, and alkoxylated methyluron. As for compounds such as urea derivatives, various resinous substances described in the above-mentioned documents can be used.

  The amount of the curable compound contained in the solid content of 100 parts by weight of the liquid resin composition is preferably 70 parts by weight or less, more preferably 3 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight. . If the amount of the curable compound is too small, the durability of the thin film formed by the obtained liquid resin composition may be insufficient, and if it exceeds 70 parts by weight, the reaction with the fluoropolymer may occur. It is difficult to avoid gelation, and the cured product may become brittle.

  The reaction between the fluorinated polymer and the curable compound is performed, for example, by adding the curable compound to a solution of an organic solvent in which the fluorinated polymer is dissolved, heating the mixture for an appropriate amount of time, and homogenizing the reaction system by stirring or the like. Just do it. The heating temperature for this reaction is preferably in the range of 30 to 150C, more preferably in the range of 50 to 120C. When the heating temperature is lower than 30 ° C., the progress of the reaction is extremely slow. When the heating temperature is higher than 150 ° C., in addition to the intended reaction, a cross-linking reaction by a reaction between a methylol group or an alkoxylated methyl group in the curable compound is caused. This is not preferable because it causes gelation. The progress of the reaction can be quantitatively determined by quantifying the methylol group or the alkoxylated methyl group by infrared spectroscopy or by collecting the dissolved polymer by a reprecipitation method and measuring the increase. Confirmation can be performed.

  For the reaction between the fluoropolymer and the curable compound, it is preferable to use an organic solvent, for example, the same organic solvent used in the production of the fluoropolymer. In the present invention, the reaction solution obtained by the fluoropolymer and the curable compound thus obtained can be used as it is as a solution of the liquid resin composition, and various additives are blended as necessary. Can also be used above.

(C) Metal oxide particles having a number average particle diameter of 100 nm or less, preferably, titanium oxide, zirconium oxide (zirconia), antimony-containing tin oxide, tin oxide-containing indium, silicon dioxide (silica), Particles mainly containing one or more metal oxides selected from aluminum oxide (alumina), cerium oxide, zinc oxide, tin oxide, antimony-containing zinc oxide and indium-containing zinc oxide can be used. Here, metal oxide particles having a multilayer structure in which the metal oxide particles are coated with one or more metal oxides other than the metal oxide may be used. Specific examples of the metal oxide particles having a multilayer structure include silica-coated titanium oxide particles, alumina-coated titanium oxide particles, and zirconia-coated titanium oxide particles. Among such metal oxide particles, particles containing silica as a main component, particles containing titanium oxide as a main component, or silica-coated titanium oxide particles are particularly preferable.
By using metal oxide particles having a multilayer structure, the photocatalytic activity of titanium oxide can be suppressed, and decomposition of a cured product can be suppressed. As a result, a cured film having a high refractive index and excellent light resistance can be obtained.
Further, by using antimony-containing tin oxide particles (ATO) or the like, an antistatic property can be imparted to the cured film. In this case, as will be described later, since the ATO particles are unevenly distributed, an effective antistatic property and good transparency can both be achieved with a smaller amount of added particles.

  As the particles containing silica as a main component, known particles can be used. If the shape is spherical, the particles are not limited to ordinary colloidal silica, but hollow particles, porous particles, core-shell particles, etc. It does not matter. Further, the particles are not limited to spherical particles, and may be irregular particles. Colloidal silica having a number average particle diameter of 1 to 100 nm, a solid content of 10 to 40% by weight, and a pH of 2.0 to 6.5 determined by a dynamic light scattering method is preferred.

The dispersion medium is preferably water or an organic solvent. Examples of the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol, and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Among them, alcohols and ketones are preferred. These organic solvents can be used alone or as a mixture of two or more.
Commercially available silica-based particles include, for example, Snowtex O manufactured by Nissan Chemical Industries, Ltd. (number-average particle diameter 7 nm determined by dynamic light scattering, solid content 20% by weight, pH 2.7). ), Snowtex OL (number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20% by weight, pH 2.5) and the like.

Further, those obtained by subjecting the surface of colloidal silica to surface treatment such as chemical modification can be used, for example, those containing a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof. Can be reacted. Examples of such a hydrolyzable silicon compound include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1 , 1-Trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. Further, a hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule include, for example, ureapropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl as those having an NH ₂ group as a reactive group. As those having an OH group, such as trimethoxysilane, bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane, etc. As those having an isocyanate group, such as 3-isocyanatopropyltrimethoxysilane, such as those having a thiocyanate group As those having an epoxy group, such as 3-thiocyanatepropyltrimethoxysilane, and the like having a thiol group, such as (3-glycidoxypropyl) trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyl trimeth Xysilane and the like can be mentioned. Preferred compounds include 3-mercaptopropyltrimethoxysilane.

The usage ratio of the metal oxide particles contained in 100 parts by weight of the solid content of the liquid resin composition is preferably 10 to 100 parts by weight, more preferably 10 to 80 parts by weight.
The use ratio of silica-based particles contained in 100 parts by weight of the solid content of the liquid resin composition is preferably 10 to 100 parts by weight, more preferably 10 to 60 parts by weight.
Further, the use ratio of the titanium oxide contained in the solid content of 100 parts by weight of the liquid resin composition, and particles containing silica-coated titanium oxide as a main component is preferably 10 to 90 parts by weight, more preferably 20 to 90 parts by weight. 80 parts by weight.

The number average particle diameter of the metal oxide particles is 100 nm or less. When the number average particle size exceeds 100 nm, it may be difficult to uniformly disperse the metal oxide particles. In addition, the metal oxide particles are likely to settle, and may lack storage stability. Furthermore, the transparency of the obtained cured film may decrease, or the turbidity (Haze value) may increase.
The number average particle diameter is more preferably from 10 to 80 nm, further preferably from 20 to 50 nm.
The “number average particle diameter” is a primary particle diameter when the metal oxide particles are agglomerated, and a long diameter (vertical) when the metal oxide particles are not spherical (for example, acicular ATO or the like). This is the average of the minor axis (horizontal).

(D) Solvent The solvent of the liquid resin composition can usually contain the solvent used for producing the fluoropolymer as it is.
In addition, a solvent can be separately added and blended for the purpose of improving the applicability of the liquid resin composition and other purposes. Preferred solvents contained in the liquid resin composition of the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. Further, in the solution of the liquid resin composition of the present invention, a solvent that cannot dissolve the fluoropolymer, for example, water, a poor solvent such as alcohols and ethers, is used in combination within a range where the fluoropolymer does not precipitate. can do. Thereby, the solution of the fluoropolymer may have good storage properties and favorable coating properties. Examples of such poor solvents include ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, ethyl cellosolve, butyl cellosolve, and the like.

(E) Additive The liquid resin composition of the present invention may have, for example, a hydroxyl group for the purpose of improving the coating properties of the liquid resin composition and the physical properties of the thin film after curing, and imparting photosensitivity to the coating film. Having various polymers and monomers, coloring agents such as pigments or dyes, stabilizers such as antioxidants and ultraviolet absorbers, thermal acid generators, photosensitive acid generators, surfactants, and various types of polymerization inhibitors Additives can be included. In particular, for the purpose of improving the hardness and durability of the formed cured film, it is preferable to add a thermal acid generator or a photoacid generator, and in particular, does not reduce the transparency of the liquid resin composition after curing. It is preferable to select and use those which are uniformly dissolved in the solution.

(1) Polymer having a hydroxyl group Examples of the polymer having a hydroxyl group that can be blended in the liquid resin composition of the present invention include, for example, copolymerizing a hydroxyl-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate. Examples of the obtained polymer, a resin having a phenol skeleton known as a novolak resin or a resol resin, and the like can be given.

(2) Colorant such as pigment or dye Examples of the colorant that can be added to the liquid resin composition of the present invention include (1) extender pigments such as alumina white, clay, barium carbonate, and barium sulfate; ) Inorganic pigments such as zinc white, lead white, graphite, lead red, ultramarine, navy blue, titanium oxide, zinc chromate, red iron, carbon black, etc .; (3) Brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow Organic dyes such as phthalocyanine blue and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acidic dyes such as roselin and methanyl yellow; Can be mentioned.

(3) Stabilizers such as antioxidants and ultraviolet absorbers As antioxidants and ultraviolet absorbers that can be added to the liquid resin composition of the present invention, known agents can be used.
Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone Monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl -4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, and the like.

  Specific examples of the ultraviolet absorber include, for example, salicylic acid-based ultraviolet absorbers represented by phenyl salicylate, benzophenone-based ultraviolet absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and benzotriazole-based ultraviolet absorbers UV absorbers used as additives for various plastics, such as cyanoacrylate UV absorbers, can be used.

(4) Thermal acid generator The thermal acid generator that can be blended in the liquid resin composition of the present invention, when heating and curing the coating film and the like of the liquid resin composition, the heating conditions, more It is a substance that can be improved to be mild. Specific examples of the thermal acid generator include, for example, various aliphatic sulfonic acids and salts thereof, citric acid, acetic acid, various aliphatic carboxylic acids and salts thereof such as maleic acid, benzoic acid, and various aromatics such as phthalic acid. Examples thereof include carboxylic acids and salts thereof, alkylbenzenesulfonic acids and ammonium salts thereof, various metal salts, and phosphoric acid esters of phosphoric acid and organic acids. The use ratio of this thermal acid generator contained in 100 parts by weight of the solid content of the liquid resin composition is preferably 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. If the ratio is excessively large, the storage stability of the liquid resin composition deteriorates, which is not preferable.

(5) Photosensitive acid generator A photosensitive acid generator that can be added to the liquid resin composition of the present invention imparts photosensitivity to a coating film of the liquid resin composition, and emits radiation such as light. It is a substance that enables photo-curing of the coating film by irradiation. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, and pyridinium salts; (2) β-ketoesters, β-sulfonyl sulfones and the like. (3) sulfonic acid esters such as alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates; and (4) sulfones represented by the following general formula (5). Imide compounds; (5) diazomethane compounds represented by the following general formula (6); and others.

式中、Ｘは、アルキレン基、アリレーン基、アルコキシレン基等の２価の基を示し、Ｒ^１は、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, X represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ¹ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. Show.

式中、Ｒ^２及びＲ^３は、互いに同一でも異なってもよく、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, R ² and R ³ may be the same or different and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group.

  The photosensitive acid generator may be used alone or in combination of two or more, and may be used in combination with the thermal acid generator. The proportion of the photosensitive acid generator used in 100 parts by weight of the solid content of the liquid resin composition is preferably 0 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. If this ratio is too large, the strength of the cured film becomes inferior and the transparency also decreases, which is not preferable.

(6) Surfactant A surfactant may be added to the liquid resin composition of the present invention for the purpose of improving the applicability of the liquid resin composition. As the surfactant, known surfactants can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, it is preferable to use a cationic surfactant in order to make the cured film have excellent strength and good optical characteristics. Further, a quaternary ammonium salt is preferable, and among them, the use of a quaternary polyether ammonium salt is particularly preferable in that dust wiping properties are further improved. Examples of the cationic surfactant which is a quaternary polyether ammonium salt include Adekacol CC-15, CC-36, CC-42 and the like manufactured by Asahi Denka Kogyo KK. The use ratio of the surfactant is preferably 5 parts by weight or less based on 100 parts by weight of the liquid resin composition.

(7) Polymerization inhibitor Examples of the thermal polymerization inhibitor that can be incorporated into the liquid resin composition of the present invention include, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, Amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and the like can be mentioned. This thermal polymerization inhibitor is preferably used in an amount of 5 parts by weight or less based on 100 parts by weight of the liquid resin composition.

2. Cured Film When a cured film is formed from the liquid resin composition of the present invention, it is preferable to coat the substrate (applied member). As such a coating method, a method such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an inkjet method can be used.

Further, means for curing the liquid resin composition is not particularly limited, but, for example, heating is preferable. In this case, it is preferable to heat at 30 to 200 ° C. for 1 to 180 minutes. By heating in this manner, a cured film having excellent antireflection properties can be obtained more efficiently without damaging the substrate or the cured film to be formed. Preferably, heating is performed at 50 to 180 ° C for 2 to 120 minutes, more preferably at 80 to 150 ° C for 5 to 60 minutes.
It can also be cured by irradiating radiation. In this case, for example, the irradiation can be performed under an irradiation condition of 0.001 to 10 J / cm ² using an ultraviolet irradiation device (a metal halide lamp, a high-pressure mercury lamp, or the like), but the irradiation condition is not limited thereto. . 0.01 to 5 J / cm ² is more preferred, and 0.1 to 3 J / cm ² is even more preferred.
Incidentally, the degree of curing of the cured film, for example, when a melamine compound is used as the curable compound, the amount of the methylol group or the alkoxylated methyl group of the melamine compound is analyzed by infrared spectroscopy, or the gelation rate, It can be quantitatively confirmed by measuring using a Soxhlet extractor.

After the application of the liquid resin composition, in the process of evaporating and drying the solvent in the composition, the metal oxide particles (C) are unevenly distributed on the undercoating side (near the boundary with the adjacent layer) or on the opposite side. Therefore, near the one side of the cured film, metal oxide particles are present at a high density, and near the other surface of the cured film, the metal oxide particles are substantially absent or present at a lower density. Then, a resin layer having a low refractive index is formed. Therefore, by curing one liquid resin composition, a cured film having a substantially two-layer structure can be obtained.
The cured film of the present invention comprises a low-refractive-index layer substantially composed of only the components (A) and (B) and a high-refractive-index layer composed of the components (A), (B) and (C). It can have a refractive index layer.

The refractive index of the obtained cured film preferably changes in the thickness direction by 0.05 to 0.8, and more preferably changes by 0.1 to 0.6. Further, it is preferable that the refractive index change has a major change near the boundary of the substantial two-layer structure.
The degree of change in the refractive index can be adjusted by the content and type of the metal oxide particles, the content and composition of the fluoropolymer, and the content and type of the curable compound.
The refractive index in the low refractive index portion of the cured film is, for example, 1.3 to 1.5, and the refractive index in the high refractive index portion is 1.6 to 2.2.

3. Laminate The liquid resin composition of the present invention can be applied in the form of a solution to various substrates, and a laminate can be obtained by curing the obtained coating film. For example, when the substrate is a transparent substrate, an excellent antireflection film is formed.
The specific structure of the antireflection film is generally a substrate, a high-refractive-index film, and a low-refractive-index film laminated in this order. The cured film obtained by curing the liquid resin composition of the present invention can form a high-refractive-index layer and a low-refractive-index layer on a base material in one step, so that the production process can be simplified. .

  The thickness of the cured film of the present invention in the antireflection film is, for example, 0.05 μm to 50 μm, but is not limited thereto.

  Specific examples of the transparent base material include, for example, triacetyl cellulose, polyethylene terephthalate resin (Lumirror manufactured by Toray Industries, Inc.), glass, polycarbonate resin, acrylic resin, styryl resin, arylate resin, norbornene-based resin (JSR Corporation) And various transparent plastic plates and films such as methyl methacrylate / styrene copolymer resin and polyolefin resin (Zeonex manufactured by Nippon Zeon Co., Ltd.). Preferred are triacetyl cellulose, polyethylene terephthalate resin (Lumirror, manufactured by Toray Industries, Inc.), and norbornene-based resin (ARTON, manufactured by JSR Corporation).

In addition, another layer may be interposed between the base material and the cured film. For example, a hard coat layer, a medium refractive index layer (refractive index: 1.5 to 1.7), and a low refractive index layer ( 1.3 to 1.5) and a high refractive index layer (1.6 to 2.2).
Further, an antistatic layer can be provided. In this case, an antireflection film having antistatic properties can be obtained without adding conductive particles such as ATO particles to a cured film obtained by curing the liquid resin composition of the present invention. In the antistatic layer, a metal oxide particle having conductivity such as ATO, or a curable film to which an organic or inorganic conductive compound is added, a metal oxide obtained by vapor-depositing or sputtering the metal oxide And a film made of a conductive organic polymer. Examples of the conductive organic polymer include a polyacetylene-based conductive polymer, a polyaniline-based conductive polymer, a polythiophene-based conductive polymer, a polypyrrole-based conductive polymer, and a polyphenylenevinylene-based conductive polymer. However, a polythiophene-based conductive polymer such as polythiophene is preferable.
One of these layers may be formed, or two or more different layers may be formed.
As a coating method of these layers, a known coating method can be used, and in particular, various methods such as a dipping method, a coater method, and a printing method can be applied.

  In addition, in order to cure the coating film of the liquid resin composition formed by coating to form a cured film having excellent optical properties and durability, it is particularly preferable to give heat history by heating. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time and the desired cured film is formed, but in practice, curing by heating is effective in shortening the required time It is a target. Further, by adding a thermal acid generator as a curing catalyst, the curing reaction can be further promoted. The curing catalyst is not particularly limited, and the above-mentioned various acids and salts thereof which are used as a curing agent for general urea resins, melamine resins, and the like can be used. In particular, ammonium salts are preferably used. Can be. The heating conditions for the curing reaction can be appropriately selected, but the heating temperature needs to be lower than the heat-resistant limit temperature of the substrate to be coated.

The cured film obtained by curing the liquid resin composition of the present invention can form a high-refractive-index layer and a low-refractive-index layer by one application step, so that the production process of the cured film can be simplified. .
Further, by unevenly distributing the metal oxide particles, the scratch resistance of the cured film can be improved.
The laminate of the present invention can be used for optical components such as a lens and a selective transmission film filter, in addition to the antireflection film.

  Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In the following description, “parts” and “%” indicate parts by weight and% by weight, respectively, unless otherwise specified.

Production Example 1
Silica-coated TiO ₂ particle dispersion (S-1)
350 parts by weight of a silica-coated titanium oxide fine powder, 80 parts by weight of an ethylene oxide-propylene oxide copolymer (average degree of polymerization: about 20), 1000 parts by weight of isopropyl alcohol, and 1000 parts by weight of butyl cellosolve are added. The dispersion was carried out for a time, and the glass beads were removed to obtain 2,430 parts by weight of a silica-coated titanium oxide particle dispersion (S-1). Here, the obtained silica-coated TiO ₂ particle dispersion was weighed on an aluminum dish and dried on a hot plate at 120 ° C. for 1 hour to determine the total solid content, which was 17% by weight. The silica-coated TiO ₂ particle dispersion-1 was weighed into a magnetic crucible, preliminarily dried on a hot plate at 80 ° C. for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain an inorganic material. When the inorganic content in the total solid content was determined from the residue amount and the total solid content concentration, it was 82% by weight.

Production Example 2
Preparation of Particles Containing Silica as Main Component The solid content is 20% by weight, the pH is 2.7, the specific surface area is 226 m ² / g by the BET method, and the silanol concentration on the silica particles determined by the methyl red adsorption method is 4. 1 × 10 ⁻⁵ mol / g, water-dispersed colloidal silica having a metal content of 4.6 ppm as Na, 0.013 ppm as Ca, and 0.011 ppm as K as determined by atomic absorption spectrometry (Nissan Chemical Industries, Ltd. ) trade name: put Snowtex -O) 30kg tank and heated to 50 ° C., the circulation flow rate of 50 l / min, at a pressure 1 kg / cm ^2, an ultrafiltration membrane module (Co. tri Tec) and alumina ultrafiltration membrane (NGK insulators, Ltd., trade name: ceramic UF element, specifications: 4 mm diameter, 19 holes, length 1 m, molecular cutoff = 150,000, membrane area = 0.24 m ² It was concentrated using. After 0.5 hour, when 10 kg of the filtrate was discharged, the solid content was 30% by weight. The average permeation flow rate (unit area of the ultrafiltration membrane, permeation weight per unit time) before the start of concentration was 90 kg / m ² / hour, and at the end of concentration was 55 kg / m ² / hour. The number average particle diameter determined by the dynamic light scattering method was 11 nm, which did not change before and after concentration.

After completion of the above process, 14 kg of methanol was added, and the mixture was concentrated at a temperature of 50 ° C., a circulating flow rate of 50 l / min, and a pressure of 1 kg / cm ² using the ultrafiltration membrane module and the ultrafiltration membrane. By repeating the discharging operation six times, methanol-dispersed colloidal silica having a solid content of 30% by weight, a water content of 1.5% by weight determined by the Karl Fischer method, and a number average particle size of 11 nm determined by the dynamic light scattering method. 20 kg were prepared. The average permeation flow rate for six runs was 60 kg / m ² / hour, and the required time was 6 hours. The specific surface area of the obtained methanol-dispersed colloidal silica by the BET method was 237 m ² / g, and the silanol concentration on the silica particles determined by the methyl red adsorption method was 3.5 × 10 ⁻⁵ mol / g.

Production Example 3
Production of silica particle sol To 20 kg of the methanol-dispersed colloidal silica prepared in Production Example 2, 0.6 kg of trimethylmethoxysilane (manufactured by Toray Dow Corning Co., Ltd.) was added, followed by heating and stirring at 60 ° C. for 3 hours. The number average particle diameter determined by the dynamic light scattering method was 11 nm, and no change was observed from that before the treatment. The specific surface area of the obtained methanol-dispersed hydrophobized colloidal silica by the BET method was 240 m ² / g, and the silanol concentration on silica particles determined by the methyl red adsorption method was 2.1 × 10 ⁻⁵ mol / g.

After completion of the above-mentioned process, 14 kg of methyl ethyl ketone (MEK) is added, concentration is performed using the ultrafiltration membrane at a temperature of 50 ° C., a circulating flow rate of 50 L / min, and a pressure of 1 kg / cm ² , and 14 kg of the filtrate is discharged. Is repeated 5 times to obtain a solid content of 30% by weight, a water content of 0.3% by weight determined by the Karl Fischer method, a methanol amount of 3.2% by weight determined by gas chromatography, and a dynamic light scattering method. 20 kg of MEK-dispersed hydrophobic colloidal silica having a number average particle diameter of 11 nm was prepared. The average permeation flow rate for five runs was 70 kg / m ² / hour, and the required time was 4 hours. The specific surface area of the obtained MEK-dispersed colloidal silica by the BET method was 230 m ² / g, and the silanol concentration on the silica particles determined by the methyl red adsorption method was 1.8 × 10 ⁻⁵ mol / g. The metal content in the solvent of the MEK-dispersed hydrophobic colloidal silica determined by the atomic absorption method was as extremely small as 0.05 ppm for Na and 0.001 ppm for Ca and K.

Production Example 4
Production of reactive silica particle sol (S-2) 3.7 parts of 3-mercaptopropyltrimethoxysilane, 93.2 parts of silica particle sol produced in Production Example 3 (28 parts as silica particles), 0.1 part of ion-exchanged water. After stirring 25 parts of the mixture at 60 ° C. for 3 hours, 2.9 parts of orthoformic acid methyl ester are added, and the mixture is further heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion liquid (S-2)). Got. After 2 g of this dispersion liquid (S-2) was weighed on an aluminum dish, it was dried on a hot plate at 175 ° C. for 1 hour and weighed, and the solid content was determined to be 31% by weight.

Production Example 5
Production of Fluorinated Polymer A stainless steel autoclave with an electromagnetic stirrer having an inner volume of 1.5 L was sufficiently substituted with nitrogen gas, and then 500 g of ethyl acetate, 43.2 g of perfluoro (propyl vinyl ether), 41.2 g of ethyl vinyl ether, and 41.2 g of hydroxyethyl vinyl ether 21.5 g, 40.5 g of "Adecaria Soap NE-30" (manufactured by Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier, and "VPS-1001" (manufactured by Wako Pure Chemical Industries, Ltd.) as an azo group-containing polydimethylsiloxane. ) 6.0 g and lauroyl peroxide 1.25 g were added, and the mixture was cooled to -50 ° C with dry ice-methanol, and oxygen in the system was removed again with nitrogen gas.
Next, 97.4 g of hexafluoropropylene was added, and the temperature was raised. The pressure at the time when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued under stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and dried at 50 ° C. under vacuum to obtain 220 g of a fluoropolymer.

  The obtained polymer had a polystyrene-equivalent number average molecular weight (Mn) of 48,000 as determined by gel permeation chromatography, a glass transition temperature (Tg) of 26.8 ° C. as determined by DSC, and a fluorine content of 50.3% as determined by the alizarin complexon method. Was confirmed.

Hereinafter, Examples 1 and 2 show preparation examples of the liquid resin composition of the present invention.
Example 1
Preparation of Liquid Resin Composition 1 24 g of the silica-coated titanium oxide dispersion (S-1) obtained in Production Example 1, 2 g of the fluoropolymer obtained in Production Example 5, and methoxylated methyl melamine “Cymel” as a crosslinkable compound No. 303 "(manufactured by Mitsui Cytec Co., Ltd.) and 0.68 g of Catalyst 4050 (manufactured by Mitsui Cytec Co., Ltd., aromatic sulfonic acid compound) as a curing catalyst were mixed with 32 g of methyl ethyl ketone as a solvent, 24 g of methyl isobutyl ketone, and tercia. The liquid resin composition 1 was obtained by dissolving in 16 g of rybutanol. The total solid content in this liquid resin composition was measured in the same manner as in Production Example 1, and it was 7.5% by weight.

Example 2
Preparation of Liquid Resin Composition 2 4.3 g of reactive silica fine powder sol (S-2) obtained in Production Example 4, 5.6 g of fluoropolymer obtained in Production Example 5, methoxylation of crosslinkable compound 1.7 g of methylmelamine "Cymel 303" (manufactured by Mitsui Cytec Co., Ltd.) and 0.63 g of Catalyst 4050 (manufactured by Mitsui Cytec Co., Ltd., aromatic sulfonic acid compound) are dissolved in 208 g of methyl ethyl ketone as a solvent. Thus, a liquid resin composition 2 was obtained. The total solid content concentration in this liquid resin composition was measured in the same manner as in Production Example 1 to find that it was 4% by weight.

Table 1 shows the compositions of the liquid resin compositions of Examples 1 and 2, and the total solid content concentration.
Hereinafter, Examples 3 to 4 show production examples of the cured film of the present invention.
Example 3
Using a wire bar coater (# 3), the liquid resin composition prepared in Example 1 was treated with an easy-adhesion-treated surface of a single-sided easily-adhesive polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm) or untreated. It was coated on the surface and dried in an oven at 120 ° C. for 10 minutes to obtain a cured film having a thickness of 0.2 μm.

Example 4
Using a wire bar coater (# 3), the liquid resin composition prepared in Example 2 was treated with an easy-adhesion treated surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm) or untreated. The surface was coated and dried in an oven at 120 ° C. for 10 minutes to obtain a cured film having a thickness of 0.1 μm.

Evaluation Examples Examples 3 and 4 The cured films obtained were evaluated according to the following criteria. Table 2 shows the results.
(1) Layer separation A 70-nm-thick section was prepared from the obtained laminate, and observed at a magnification of 30,000 times with a transmission electron microscope (manufactured by JEOL Ltd., model JEM-2010F). The evaluation was based on the following criteria. Table 2 shows the obtained results.
A: The cured layer of the liquid resin composition of the present invention is clearly separated into a layer having metal oxide particles at a high density and a layer having substantially no metal oxide particles.
Δ: There is a density difference of the metal oxide particles in the thickness direction of the layer, but the separation of the two layers is unclear.
×: metal oxide particles are substantially uniformly distributed.

(2) Turbidity Turbidity (Haze value) of the obtained laminate was measured using a Haze meter, and evaluated based on the following criteria. Table 2 shows the obtained results.
：: Haze value is 1% or less.
Δ: Haze value is 3% or less.
X: Haze value is 5% or more.

(3) Adhesion The obtained cured film was subjected to a grid test in accordance with JIS K5400, and evaluated according to the following criteria. Table 2 shows the obtained results.
：: No peeling was observed on 100 crosses.
Δ: Peeling of 1 to 3 crosses was observed in 100 crosses.
×: Peeling of four or more grids was observed in 100 grids.

(4) Anti-reflection property The anti-reflection property of the obtained anti-reflection laminate was measured using a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi, Ltd. And the reflectance was measured and evaluated in the wavelength range of 340 to 700 nm. Specifically, the reflectance of the anti-reflection laminate (anti-reflection film) at each wavelength is measured with the reflectance of the deposited aluminum film as a reference (100%). The antireflection property was evaluated according to the following criteria.
：: The reflectance is 0.5% or less.
Δ: The reflectance is 1% or less.
X: The reflectance is 2% or less.

(5) Scratch resistance test (steel wool resistance test)
The steel wool resistance test of the cured film was performed by the following method. That is, steel wool (Bonstar No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin-type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was subjected to a load of 200 g. Were repeatedly rubbed 10 times under the conditions described above, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria.
A: Almost no peeling of the cured film or generation of scratches was observed.
：: Fine scratches are observed on the cured film.
×: Peeling occurred on a part of the cured film, or streaky scratches occurred on the surface of the cured film.

(6) Evaluation of dust wiping properties Under an environment of a temperature of 23 ° C and a relative humidity of 30%, the entire surface of the cured film was uniformly folded with a nonwoven fabric (BEMCOT S-2 manufactured by Asahi Kasei Kogyo Co., Ltd.) five times, and then chopped cellulose fibers were sprayed. The sample surface was wiped with a clean non-woven fabric. The remaining amount of the chopped fibers adhering to the surface of the cured film was visually confirmed according to the following criteria.
A: Shredded fibers are almost completely wiped off.
：: Little chopped fibers remained on the sample surface without being wiped off.
×: Most of the chopped fibers remain on the sample surface without being wiped.

  The cured film obtained by curing the liquid resin composition of the present invention can form a low-refractive-index layer and a high-refractive-index layer in a single application step, so that a cured film having a two-layer structure is produced. The process can be simplified. Therefore, the liquid resin composition of the present invention can be advantageously used particularly for forming an optical material such as an antireflection film and an optical fiber sheath material, and is required to have weather resistance by utilizing its high fluorine content. It can be suitably used as a material for a paint, a material for a weather-resistant film, a material for a coating, etc. for a substrate to be formed. Moreover, the cured film is excellent in adhesion to a substrate, has high scratch resistance, and imparts a good antireflection effect. Therefore, the cured film is extremely useful as an antireflection film, and can be applied to various display devices. And its visibility can be improved.

Claims (12)

A liquid resin composition comprising the following components (A), (B), (C) and (D).
(A) Fluoropolymer (B) Curable compound (C) Metal oxide particles having a number average particle diameter of 100 nm or less (D) Solvent   The metal oxide particles are selected from titanium oxide, zirconium oxide, antimony-containing tin oxide, tin oxide-containing indium, silicon dioxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, antimony-containing zinc oxide, and indium-containing zinc oxide. The liquid resin composition according to claim 1, wherein the liquid resin composition is particles containing one or more metal oxides as main components.   The liquid resin composition according to claim 1, wherein the metal oxide particles are metal oxide particles having a multilayer structure.   A cured film obtained by curing the liquid resin composition according to claim 1.   The cured film has a two-layer structure including a layer in which the component (C) exists at a high density and a layer in which the component (C) does not substantially exist or exists at a low density. Item 6. The cured film according to Item 4.   A method for producing a cured film, comprising a step of curing the liquid resin composition according to any one of claims 1 to 3 by heating or irradiating radiation.   A laminate comprising at least one layer comprising the cured film according to claim 4 on a substrate.   The laminate according to claim 7, further comprising another layer between the layer made of the cured film and the substrate.   The other layer includes a hard coat layer, a layer having a refractive index of 1.5 to 1.7, and a combination of a layer having a refractive index of 1.3 to 1.5 and a layer having a refractive index of 1.6 to 2.2. The laminate according to claim 8, comprising one or more layers selected from the group.   The said base material layer consists of triacetyl cellulose, a polyethylene terephthalate resin, a polycarbonate resin, an acrylic resin, an acryl / styrene copolymer resin, a polyolefin resin, a norbornene resin resin, or glass, The glass of Claim 7-9 characterized by the above-mentioned. The laminate according to any one of the above.   The laminate according to any one of claims 7 to 10, which is an optical component.   The laminate according to any one of claims 7 to 10, which is used for an antireflection film.